EP1016728A2 - Process for producing a syrup rich in maltose - Google Patents

Process for producing a syrup rich in maltose Download PDF

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Publication number
EP1016728A2
EP1016728A2 EP99403287A EP99403287A EP1016728A2 EP 1016728 A2 EP1016728 A2 EP 1016728A2 EP 99403287 A EP99403287 A EP 99403287A EP 99403287 A EP99403287 A EP 99403287A EP 1016728 A2 EP1016728 A2 EP 1016728A2
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EP
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Prior art keywords
maltose
syrup
rich
maltitol
fraction
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Granted
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EP99403287A
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German (de)
French (fr)
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EP1016728A3 (en
EP1016728B1 (en
Inventor
Jean-Jacques Caboche
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Roquette Freres SA
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Roquette Freres SA
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/22—Preparation of compounds containing saccharide radicals produced by the action of a beta-amylase, e.g. maltose
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/18—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic polyhydric

Definitions

  • the invention relates to a method of manufacturing a syrup rich in maltose. It also concerns the use a maltose-rich syrup obtained by the conforming process to the present invention for the manufacture of a syrup rich in maltitol. It also relates to the use of a maltose-rich syrup obtained by the process in accordance with present invention for the manufacture of maltitol crystallized.
  • the document FR-A-2.000.580 describes a method of preparation of a syrup with a high maltitol content by hydrogenation of a syrup with a high maltose content which is obtained by liquefying a low content starch milk dry matter to a lower dextrose-equivalent at 2, the product thus obtained being saccharified under the action of specific enzymes.
  • the syrup obtained contains proportions of polymers of degree of polymerization (DP, in the rest of the description) greater than or equal to 4, which are troublesome.
  • maltogenic ⁇ -amylase allows effectively and advantageously to lower the proportion in maltotriose by hydrolysis of the latter into maltose and glucose, it nevertheless has the major drawback of generate significant amounts of glucose, and possibly sorbitol in case of hydrogenation of hydrolysates. Indeed, the residual glucose obtained after saccharification of liquefied starch milk is added a significant proportion of glucose from the hydrolysis of maltotriose by maltogenic ⁇ -amylase.
  • glucose or sorbitol free in maltose or maltitol syrups cause other disadvantages such as lowering of the equilibrium viscosity and relative humidity of products in which they are incorporated as sugar substitutes.
  • syrups with very high maltose content could be made in performing molecular sieving of starch milk liquefied and saccharified so as to collect a fraction enriched in maltose and a fraction enriched in glucose then by bringing said enriched fraction into contact in maltose with a maltogenic ⁇ -amylase.
  • an effective action of ⁇ -amylase maltogenic can only be obtained from a liquefied and saccharified starch milk having a composition particular, presenting in particular a spectrum bimodal carbohydrate, i.e. having next to a high maltose content and appreciably high in oligosaccharides, high glucose content.
  • the particular bimodal carbohydrate spectrum of milk of liquefied and saccharified starch is obtained, in accordance to the process of the invention, by performing on the latter a molecular sieving step.
  • the first step of the process according to the invention is in itself known. It consists in liquefying a milk starch whose botanical origin may be arbitrary: it can come from wheat, corn or potato by example.
  • This starch milk is supplemented with acid in the case of a so-called acid liquefaction, or of an ⁇ -amylase in the case of an enzymatic liquefaction.
  • the process according to the invention it is preferred to carry out a controlled hydrolysis of the starch milk so as to obtain a liquefied starch milk with a low conversion rate.
  • the conditions of temperature, pH, level of enzyme and calcium known to a person skilled in the art, are determined in such a way that they make it possible to obtain a DE (Dextrose Equivalent) less than 10, preferably less than 6, and more particularly less than 4.
  • the liquefaction stage is carried out in two sub-stages, the first consisting in heating, for a few minutes and at a temperature between 105 and 108 ° C., the starch milk in the presence of an ⁇ -amylase (type TERMAMYL R 120L sold by the company NOVO) and a calcium-based activator, the second consisting in heating the starch milk thus treated to a temperature between 95 and 100 ° C for one to two hours.
  • an ⁇ -amylase type TERMAMYL R 120L sold by the company NOVO
  • the ⁇ -amylase is inhibited.
  • This inhibition ⁇ -amylase can preferably be done by the thermal, by carrying out a liquefaction outlet with a shock thermal for a few seconds at a higher temperature or equal to 130 ° C.
  • the milk is then saccharified starch liquefied by means of a ⁇ -amylase such as that marketed by GENENCOR under the name SPEZYME® BBA 1500.
  • a ⁇ -amylase such as that marketed by GENENCOR under the name SPEZYME® BBA 1500.
  • This addition of debranching enzyme can be done at when adding ⁇ -amylase or when adding maltogenic ⁇ -amylase.
  • the debranching enzyme is chosen in the group consisting of pullulanases and isoamylases.
  • Pullulanase is, for example, that marketed by ABM under the name PULLUZYME® 750L.
  • the isoamylase is, for example, that marketed by the company HAYASHIBARA.
  • the method according to the invention is implemented in the presence of isoamylase for which the Applicant company has found that it allows to obtain a maltose syrup having a content of higher maltose than using pullulanase.
  • the saccharification stage can be carried out also totally or partially in the presence of ⁇ -amylase fungal using, for example, SPEZYME® DBA 1500 (marketed by GENENCOR) instead and place de la SPEZYME® BBA 1500 (marketed by the same society).
  • SPEZYME® DBA 1500 marketed by GENENCOR
  • de la SPEZYME® BBA 1500 marketed by the same society.
  • ⁇ -amylase saccharification is carried out possibly associated with the disconnecting enzyme until the maltose hydrolyzate contains at least 75% by weight of maltose and preferably about 80% by weight maltose. It lasts at least 24 hours.
  • hydrolyzate thus saccharified is then filtered on pre-layer or microfiltration filter on membranes, then demineralized and concentrated.
  • the process according to the invention is performs molecular sieving of liquefied starch milk and saccharified so as to collect a fraction enriched in maltose and a fraction enriched in glucose.
  • the fraction enriched in maltose with a maltogenic ⁇ -amylase is advantageously that marketed by the company NOVO, under the names Maltogenase® 4000L and NOVAMYL®.
  • the molecular sieving step implemented in the process according to the invention may consist, for example, in a chromatographic separation step or in a separation step on membranes.
  • the chromatographic fractionation step is carried out in a manner known per se, discontinuously or continuous (simulated moving bed), on adsorbents of the type cationic resins, or on strongly acidic zeolites, preferentially charged using alkaline ions or alkaline earth such as calcium or magnesium but more preferably using sodium ions.
  • Membranes different pore diameters are made from many polymers and copolymers of the polysulfone type, polyamides, polyacrylonitrates, polycarbonates, polyfurans, etc.
  • the non-maltose part from membranes or chromatography comprising the fraction enriched in glucose, is recycled upstream of the saccharification.
  • the pressure of hydrogen used is generally between 30 and 60 bars and the temperature at which it takes place the hydrogenation is between 100 and 150 ° C.
  • the reaction is stopped when the content of the medium reaction in reducing sugars has become less than 1%, preferably still less than 0.5% and more particularly less than 0.1%.
  • the reaction medium After the reaction medium has cooled, remove the catalyst by filtration and demineralize the maltitol syrup thus obtained on cationic resins and anionic. At this point, the syrups contain at least 93% maltitol.
  • the maltitol syrup obtained in the hydrogenation stage previous can then undergo a crystallization step of so as to obtain crystallized maltitol.
  • the use according to the invention of syrup rich in maltose for the manufacturing crystallized maltitol makes it possible to reduce very importantly (up to 80% compared to a process the quantities of mother liquors (i.e. the fraction depleted in maltitol) generated during the sieving step molecular downstream of the crystallization step.
  • Starch milk with a dry matter content of 31%, is conventionally liquefied using 0.2% TERMAMYL® 120L ( ⁇ -amylase marketed by the company NOVO) at a pH of 5.7 to 6.5 to a slightly ED less than 4.
  • reaction medium is then heated for a few seconds at 140 ° C. so as to inhibit ⁇ -amylase, then we adjust the pH between 5 and 5.5 and the temperature at 55 ° C.
  • the saccharification is carried out with a dry matter 25%, or slightly lower, in the presence of pullulanase (PULLUZYME® 750L sold by the company ABM) and ⁇ -amylase (SPEZYME® BBA marketed by the GENENCOR) at respective doses of 0.1% and 0.05 % on dry matter.
  • pullulanase PULLUZYME® 750L sold by the company ABM
  • SPEZYME® BBA ⁇ -amylase
  • the saccharification which lasts about 48 hours, gives a hydrolyzate showing the following composition, DP1: 1.4 %, DP2: 82.4%, DP3: 13.2%, DP4 and more: 2.6%.
  • the hydrolyzate then undergoes a conventional purification by filtration, discoloration and demineralization then is concentrated to around 20% dry matter and adjusted to pH 5.5.
  • a continuous chromatography step is carried out on the maltose hydrolyzate thus obtained in the manner next.
  • the fractions are recovered enriched with maltose of the following composition: DP1: 1.5%, DP2: 94%, DP3: 4.5%.
  • the chromatographic maltose yield is 91.5 %.
  • the composition of the maltose syrup obtained is as follows: DP1: 4%, DP2: 95.5%, DP3: 0.5%.
  • the maltose syrup obtained in Example 1 above is subjected to a maltose crystallization stage of the next way.
  • the maltose solution is seeded with 5% by weight of maltose crystal sprouts and cools the solution 75 ° C to 40 ° C, 0.5 ° C per hour, shaking the solution at 50 rpm in a double crystallizer wall.
  • the crystals are separated mother liquor using a centrifugal wringer conventional.
  • the crystallization yield is 50% by weight expressed by weight of crystallized maltose on the weight of starting maltose.
  • the maltose purity of the crystals recovered is 97.5% on dry.
  • the water content is 5%.
  • the maltose syrup from Example 1 is demineralized and then hydrogenated under the following conditions: Dry matter 40% Temperature 115 ° C Catalyst dose 5% dry P / P H 2 pressure 50 bars
  • the reaction is stopped when the reducing sugars are less than 0.3%.
  • the medium is then filtered, demineralized and concentrated to 85% dry matter; its composition is: Sorbitol 5.5% Maltitol 94.0% Hydrogenated superiors 0.5%
  • the crystals After turbination, the crystals are dried and have a richness of 99.7%; the mother liquors are adjusted to 60% dry matter and chromatographed.
  • the maltitol-depleted fraction containing 53.5% of sorbitol, 42.5% maltitol and 4% superior hydrogenated, is then subjected to a hydrolysis step acid.
  • the hydrolysis of the depleted fraction is carried out continuously, on a cation exchange resin, of type C145 from Purolite, in H + form placed in a column thermostatically controlled at 115 ° C; by feeding the column at 1 bv / h with the concentrated solution at 40%, the following composition is obtained: sorbitol: 70.5%; maltitol: 12.3%; higher: 0.4%; glucose: 16.8%.
  • This solution is then demineralized and hydrogenated under the following conditions: Dry matter 40% Temperature 135 ° C Catalyst dose 5% P / Psec Hydrogen pressure 50 bars, until a rate of free reducing sugars of less than 0.1% is obtained.

Abstract

A process for the manufacture of a maltose rich syrup is new and comprises liquefying and saccharifying a starch milk in the presence of beta -amylase and at lest one debranching enzyme e.g. pullulanases and/or isoamylases, filtering the solution and recovering the maltose and glucose enriched fractions and contacting the maltose rich solution with a maltogenic alpha -amylase to obtain the maltose rich syrup. Independent claims are also included for the following: (1) manufacture of a maltose rich syrup comprising: (a) liquefaction of a starch milk; (b) saccharification of the starch milk in the presence of a beta -amylase; (c) filtering the starch milk to recover maltose and glucose and maltose enriched fractions; (d) contacting the maltose rich fraction with a maltogenic alpha -amylase and at least one debranching enzyme e.g. pullulanases and/or isoamylases for obtaining the maltose rich syrup; and (2) the manufacture of crystallized maltose comprising crystallizing maltose rich syrup.

Description

L'invention concerne un procédé de fabrication d'un sirop riche en maltose. Elle concerne aussi l'utilisation d'un sirop riche en maltose obtenu par le procédé conforme à la présente invention pour la fabrication d'un sirop riche en maltitol. Elle concerne encore l'utilisation d'un sirop riche en maltose obtenu par le procédé conforme à la présente invention pour la fabrication de maltitol cristallisé.The invention relates to a method of manufacturing a syrup rich in maltose. It also concerns the use a maltose-rich syrup obtained by the conforming process to the present invention for the manufacture of a syrup rich in maltitol. It also relates to the use of a maltose-rich syrup obtained by the process in accordance with present invention for the manufacture of maltitol crystallized.

On connaít déjà des procédés permettant d'obtenir des sirops riches en maltose. Parmi ces procédés, on peut notamment citer celui décrit par HODGE et Coll. dans "Cereal Chemistry" n° 25, pages 19-30, janvier 1948, et qui comprend une étape de précipitation des dextrines limites par des solutions alcooliques et celui décrit par WOLFROM et THOMPSON dans "Methods in carbohydrate chemistry", 1962, pages 334-335.We already know methods for obtaining maltose-rich syrups. Among these methods, one can in particular, cite the one described by HODGE et al. in "Cereal Chemistry" n ° 25, pages 19-30, January 1948, and which includes a step for precipitating limit dextrins by alcoholic solutions and that described by WOLFROM and THOMPSON in "Methods in carbohydrate chemistry", 1962, pages 334-335.

D'autres procédés de fabrication de sirops riches en maltose ont encore été proposés comprenant une étape d'adsorption sur charbon des dextrines (US-A-4.194.623), une étape de chromatographie sur zéolithes ou résines cationiques ou anioniques (FR-A-2.510.581), une étape d'ultrafiltration des sirops de maltose (US-A-4.429.122), l'utilisation combinée de plusieurs enzymes différentes, à savoir une α-amylase, une β-amylase et une isoamylase ou une pullulanase (FR-A-2.012.831).Other methods of making syrups rich in maltose have also been proposed including a step dextrin adsorption on carbon (US-A-4,194,623), a step of chromatography on zeolites or resins cationic or anionic (FR-A-2.510.581), one step ultrafiltration of maltose syrups (US-A-4,429,122), the combined use of several different enzymes, to know an α-amylase, a β-amylase and an isoamylase or a pullulanase (FR-A-2,012,831).

Cette dernière technique présente, par rapport aux précédentes, de nombreux avantages. Elle souffre néanmoins de certains inconvénients, dont notamment celui résidant dans le fait que les saccharifications doivent être effectuées à des teneurs en matières sèches très basses, de l'ordre de 20 g/l, pour obtenir une efficacité d'hydrolyse maximum des enzymes. This last technique presents, compared to many advantages. She nevertheless suffers certain disadvantages, including that of the resident in the fact that the saccharifications must be carried out at very low dry matter contents, around 20 g / l, to obtain hydrolysis efficiency maximum of enzymes.

Le document FR-A-2.000.580 décrit un procédé de préparation d'un sirop à teneur élevée en maltitol par hydrogénation d'un sirop à teneur élevée en maltose qui est obtenu par liquéfaction d'un lait d'amidon à faible teneur en matières sèches jusqu'à un dextrose-équivalent inférieur à 2, le produit ainsi obtenu étant saccharifié sous l'action d'enzymes spécifiques.The document FR-A-2.000.580 describes a method of preparation of a syrup with a high maltitol content by hydrogenation of a syrup with a high maltose content which is obtained by liquefying a low content starch milk dry matter to a lower dextrose-equivalent at 2, the product thus obtained being saccharified under the action of specific enzymes.

Ce procédé est coûteux, d'un rendement médiocre et donne lieu à des problèmes de contamination bactérienne et à des phénomènes de rétrogradation de l'amylose. En outre, le sirop obtenu contient des proportions de polymères de degré de polymérisation (DP, dans la suite de la description) supérieur ou égal à 4, qui sont gênantes.This process is costly, of poor performance and gives rise to problems of bacterial contamination and to retrogradation phenomena of amyloidosis. In addition, the syrup obtained contains proportions of polymers of degree of polymerization (DP, in the rest of the description) greater than or equal to 4, which are troublesome.

Plus récemment, le document US-A-5.141.859 a proposé un procédé de fabrication d'un sirop à teneur élevée en maltose, mettant en oeuvre deux étapes successives de saccharification. Ce document préconise en effet un procédé comprenant une première étape de saccharification en présence d'une β-amylase et une étape subséquente de saccharification en présence d'une α-amylase maltogénique. Selon ce document, l'α-amylase maltogénique est utilisée, après la première étape de saccharification à la β-amylase, pour hydrolyser les oligosaccharides (de DP3 à DP7) et essentiellement le maltotriose (trisaccharide), en maltose et glucose.More recently, document US-A-5,141,859 has proposed a method of manufacturing a syrup with a high content of maltose, implementing two successive stages of saccharification. This document indeed recommends a process including a first saccharification stage in presence of a β-amylase and a subsequent step of saccharification in the presence of a maltogenic α-amylase. According to this document, maltogenic α-amylase is used, after the first step of β-amylase saccharification, to hydrolyze oligosaccharides (from DP3 to DP7) and mainly maltotriose (trisaccharide), in maltose and glucose.

Si l'utilisation d'α-amylase maltogénique permet effectivement et avantageusement d'abaisser la proportion en maltotriose par hydrolyse de ce dernier en maltose et glucose, elle présente néanmoins l'inconvénient majeur de générer des quantités importantes de glucose, et éventuellement de sorbitol en cas d'hydrogénation des hydrolysats. En effet, au glucose résiduel obtenu après saccharification du lait d'amidon liquéfié vient s'ajouter une proportion importante de glucose issu de l'hydrolyse du maltotriose par l'α-amylase maltogénique. If the use of maltogenic α-amylase allows effectively and advantageously to lower the proportion in maltotriose by hydrolysis of the latter into maltose and glucose, it nevertheless has the major drawback of generate significant amounts of glucose, and possibly sorbitol in case of hydrogenation of hydrolysates. Indeed, the residual glucose obtained after saccharification of liquefied starch milk is added a significant proportion of glucose from the hydrolysis of maltotriose by maltogenic α-amylase.

Ces quantités importantes de glucose, donc de sorbitol après hydrogénation, rendent la cristallisation du maltitol plus difficile et conduisent à une baisse de la richesse des cristaux, rendant ceux-ci mal adaptés à certaines applications comme par exemple la fabrication de chocolat.These large amounts of glucose, so sorbitol after hydrogenation, make the crystallization of maltitol more difficult and lead to a decline in wealth crystals, making them ill-suited to certain applications such as making chocolate.

En outre, la persistance de glucose ou de sorbitol libres dans les sirops de maltose ou de maltitol occasionnent d'autres inconvénients tels qu'un abaissement de la viscosité et de l'humidité relative d'équilibre des produits dans lesquels ils sont incorporés en tant que succédanés du sucre.In addition, the persistence of glucose or sorbitol free in maltose or maltitol syrups cause other disadvantages such as lowering of the equilibrium viscosity and relative humidity of products in which they are incorporated as sugar substitutes.

Consciente qu'il existe un intérêt croissant pour les produits à très haute teneur en maltose, la Société Demanderesse a conduit de nombreuses recherches dans le but de mettre au point un procédé économique et extrêmement fiable permettant d'obtenir de tels produits.Aware that there is a growing interest in products with very high maltose content, the Company Applicant has conducted numerous searches with the aim to develop an economical and extremely reliable for obtaining such products.

D'une manière extrêmement simple et particulièrement efficace au regard de tout ce qui a été proposé à ce jour, la Société Demanderesse a constaté que des sirops à très haute teneur en maltose pouvaient être fabriqués en effectuant un tamisage moléculaire d'un lait d'amidon liquéfié et saccharifié de manière à recueillir une fraction enrichie en maltose et une fraction enrichie en glucose puis en mettant en contact ladite fraction enrichie en maltose avec une α-amylase maltogénique.In an extremely simple and particularly effective with regard to all that has been proposed to date, the Applicant Company has found that syrups with very high maltose content could be made in performing molecular sieving of starch milk liquefied and saccharified so as to collect a fraction enriched in maltose and a fraction enriched in glucose then by bringing said enriched fraction into contact in maltose with a maltogenic α-amylase.

L'invention propose donc un procédé de fabrication d'un sirop riche en maltose, comprenant les étapes successives consistant à :

  • (a) effectuer une liquéfaction d'un lait d'amidon ;
  • (b) effectuer une saccharification du lait d'amidon liquéfié en présence d'une β-amylase et d'au moins une enzyme débranchante choisie dans le groupe constitué par les pullulanases et les isoamylases ;
  • (c) effectuer un tamisage moléculaire du lait d'amidon liquéfié et saccharifié de manière à recueillir une fraction enrichie en maltose et une fraction enrichie en glucose ;
  • (d) mettre en contact ladite fraction enrichie en maltose avec une α-amylase maltogénique en vue de l'obtention d'un sirop riche en maltose.
    • The invention therefore proposes a method for manufacturing a syrup rich in maltose, comprising the successive stages consisting in:
  • (a) carrying out a liquefaction of a starch milk;
  • (b) carrying out a saccharification of the liquefied starch milk in the presence of a β-amylase and at least one debranching enzyme chosen from the group consisting of pullulanases and isoamylases;
  • (c) carrying out molecular sieving of the liquefied and saccharified starch milk so as to collect a fraction enriched in maltose and a fraction enriched in glucose;
  • (d) bringing said maltose-enriched fraction into contact with a maltogenic α-amylase with a view to obtaining a syrup rich in maltose.

    • L'invention propose également un procédé de fabrication d'un sirop riche en maltose, comprenant les étapes successives consistant à :

  • (a) effectuer une liquéfaction d'un lait d'amidon ;
  • (b) effectuer une saccharification du lait d'amidon liquéfié en présence d'une β-amylase ;
  • (c) effectuer un tamisage moléculaire du lait d'amidon liquéfié et saccharifié de manière à recueillir une fraction enrichie en maltose et une fraction enrichie en glucose ;
  • (d) mettre en contact ladite fraction enrichie en maltose avec une α-amylase maltogénique et au moins une enzyme débranchante choisie dans le groupe constitué par les pullulanases et les isoamylases en vue de l'obtention d'un sirop riche en maltose.
    • The invention also provides a method for manufacturing a syrup rich in maltose, comprising the successive steps consisting in:
  • (a) carrying out a liquefaction of a starch milk;
  • (b) carrying out a saccharification of the liquefied starch milk in the presence of a β-amylase;
  • (c) carrying out molecular sieving of the liquefied and saccharified starch milk so as to collect a fraction enriched in maltose and a fraction enriched in glucose;
  • (d) bringing said maltose-enriched fraction into contact with a maltogenic α-amylase and at least one debranching enzyme chosen from the group consisting of pullulanases and isoamylases with a view to obtaining a syrup rich in maltose.

    • Le procédé de fabrication d'un sirop de maltose objet de la présente invention, repose en fait sur un constat simple, négligé jusqu'alors, selon lequel l'action d'une enzyme spécifique sur un substrat déterminé n'est efficace que si les caractéristiques du substrat, en tant que telles, permettent effectivement son action.The process for making an object maltose syrup of the present invention, is in fact based on an observation simple, neglected until now, according to which the action of a specific enzyme on a specific substrate is only effective that if the characteristics of the substrate, as such, actually allow its action.

    Dans le cas présent, une action efficace de l'α-amylase maltogénique ne peut être obtenue qu'à partir d'un lait d'amidon liquéfié et saccharifié ayant une composition particulière, présentant en particulier un spectre glucidique bimodal, à savoir présentant à côté d'une haute teneur en maltose et sensiblement élevée en oligosaccharides, une teneur élevée en glucose.In this case, an effective action of α-amylase maltogenic can only be obtained from a liquefied and saccharified starch milk having a composition particular, presenting in particular a spectrum bimodal carbohydrate, i.e. having next to a high maltose content and appreciably high in oligosaccharides, high glucose content.

    On cherche donc, dans la présente invention, à ce que les impuretés se présentent sous la forme de glucose plutôt que sous forme d'oligosaccharides, et en particulier de maltotriose, de masse moléculaire proche du maltose.It is therefore sought, in the present invention, to ensure that impurities come in the form of glucose rather as in the form of oligosaccharides, and in particular of maltotriose, of molecular mass close to maltose.

    Le spectre glucidique bimodal particulier du lait d'amidon liquéfié et saccharifié est obtenu, conformément au procédé de l'invention, en effectuant sur ce dernier une étape de tamisage moléculaire.The particular bimodal carbohydrate spectrum of milk of liquefied and saccharified starch is obtained, in accordance to the process of the invention, by performing on the latter a molecular sieving step.

    La première étape du procédé conforme à l'invention est en soi connue. Elle consiste à liquéfier un lait d'amidon dont l'origine botanique peut être quelconque : il peut provenir du blé, du maïs ou de la pomme de terre par exemple.The first step of the process according to the invention is in itself known. It consists in liquefying a milk starch whose botanical origin may be arbitrary: it can come from wheat, corn or potato by example.

    Ce lait d'amidon ou de fécule est additionné d'acide dans le cas d'une liquéfaction dite acide, ou d'une α-amylase dans le cas d'une liquéfaction enzymatique.This starch milk is supplemented with acid in the case of a so-called acid liquefaction, or of an α-amylase in the case of an enzymatic liquefaction.

    Dans le procédé conforme à l'invention, on préfère effectuer une hydrolyse ménagée du lait d'amidon de façon à obtenir un lait d'amidon liquéfié à faible taux de transformation. Ainsi, les conditions de température, de pH, de taux d'enzyme et de calcium, connues de l'homme du métier, sont déterminées de manière telle qu'elles permettent d'obtenir un DE (Dextrose Equivalent) inférieur à 10, de préférence inférieur à 6, et plus particulièrement inférieur à 4.De préférence, l'étape de liquéfaction est conduite en deux sous-étapes, la première consistant à chauffer, pendant quelques minutes et à une température comprise entre 105 et 108°C, le lait d'amidon en présence d'une α-amylase (type TERMAMYLR 120L commercialisée par la société NOVO) et d'un activateur à base de calcium, la seconde consistant à chauffer le lait d'amidon ainsi traité à une température comprise entre 95 et 100°C pendant une à deux heures.In the process according to the invention, it is preferred to carry out a controlled hydrolysis of the starch milk so as to obtain a liquefied starch milk with a low conversion rate. Thus, the conditions of temperature, pH, level of enzyme and calcium, known to a person skilled in the art, are determined in such a way that they make it possible to obtain a DE (Dextrose Equivalent) less than 10, preferably less than 6, and more particularly less than 4. Preferably, the liquefaction stage is carried out in two sub-stages, the first consisting in heating, for a few minutes and at a temperature between 105 and 108 ° C., the starch milk in the presence of an α-amylase (type TERMAMYL R 120L sold by the company NOVO) and a calcium-based activator, the second consisting in heating the starch milk thus treated to a temperature between 95 and 100 ° C for one to two hours.

    Une fois l'étape de liquéfaction terminée, dans les conditions de teneur en matières sèches, de pH, de taux d'enzyme et de calcium bien connues de l'homme du métier, on procède à l'inhibition de l'α-amylase. Cette inhibition de l'α-amylase peut se faire de préférence par voie thermique, en procédant en sortie de liquéfaction à un choc thermique de quelques secondes à une température supérieure ou égale à 130°C.Once the liquefaction stage is complete, within dry matter content, pH, rate conditions enzyme and calcium well known to those skilled in the art, the α-amylase is inhibited. This inhibition α-amylase can preferably be done by the thermal, by carrying out a liquefaction outlet with a shock thermal for a few seconds at a higher temperature or equal to 130 ° C.

    On effectue ensuite la saccharification du lait d'amidon liquéfié au moyen d'une β-amylase telle que celle commercialisée par la société GENENCOR sous la dénomination SPEZYME® BBA 1500.The milk is then saccharified starch liquefied by means of a β-amylase such as that marketed by GENENCOR under the name SPEZYME® BBA 1500.

    Lors de cette étape, il convient d'associer à la β-amylase une enzyme hydrolysant spécifiquement les liaisons α-1,6 de l'amidon. Cet ajout d'une enzyme débranchante permet d'une part d'accélérer les réactions d'hydrolyse sans simultanément accélérer les réactions de réversion et, d'autre part, de réduire la quantité d'oligosaccharides hautement branchés résistant normalement à l'action des enzymes maltogéniques.During this stage, it is advisable to associate with β-amylase an enzyme specifically hydrolyzing bonds α-1,6 of starch. This addition of a debranching enzyme on the one hand accelerates the hydrolysis reactions without simultaneously accelerating the reversion reactions and, on the other hand, to reduce the amount of oligosaccharides highly connected normally resistant to the action of maltogenic enzymes.

    Cet ajout d'enzyme débranchante peut se faire au moment de l'ajout de la β-amylase ou au moment de l'ajout de l'α-amylase maltogénique.This addition of debranching enzyme can be done at when adding β-amylase or when adding maltogenic α-amylase.

    Selon l'invention, l'enzyme débranchante est choisie dans le groupe constitué par les pullulanases et les isoamylases. La pullulanase est, par exemple, celle commercialisée par la société ABM sous la dénomination PULLUZYME® 750L. L'isoamylase est, par exemple, celle commercialisée par la société HAYASHIBARA.According to the invention, the debranching enzyme is chosen in the group consisting of pullulanases and isoamylases. Pullulanase is, for example, that marketed by ABM under the name PULLUZYME® 750L. The isoamylase is, for example, that marketed by the company HAYASHIBARA.

    Avantageusement, le procédé conforme à l'invention est mis en oeuvre en présence d'isoamylase pour laquelle la Société Demanderesse a constaté qu'elle permettait d'obtenir un sirop de maltose présentant une teneur en maltose plus élevée qu'en utilisant une pullulanase.Advantageously, the method according to the invention is implemented in the presence of isoamylase for which the Applicant company has found that it allows to obtain a maltose syrup having a content of higher maltose than using pullulanase.

    Dans un mode de réalisation particulier de l'invention, l'étape de saccharification peut être conduite également totalement ou partiellement en présence d'α-amylase fongique en utilisant, par exemple, la SPEZYME® DBA 1500(commercialisée par la société GENENCOR) en lieu et place de la SPEZYME® BBA 1500(commercialisée par la même société).In a particular embodiment of the invention, the saccharification stage can be carried out also totally or partially in the presence of α-amylase fungal using, for example, SPEZYME® DBA 1500 (marketed by GENENCOR) instead and place de la SPEZYME® BBA 1500 (marketed by the same society).

    En fin de saccharification, il est possible d'ajouter un peu d'α-amylase, ce qui améliore généralement les étapes subséquentes de filtration. Les quantités et les conditions d'action des différentes enzymes mises en oeuvre dans les étapes de liquéfaction et de saccharification du lait d'amidon sont généralement celles qui sont recommandées pour l'hydrolyse de l'amidon et sont bien connues de l'homme du métier.At the end of saccharification, it is possible to add a little α-amylase, which generally improves the stages subsequent filtration. Quantities and conditions of action of the different enzymes used in milk liquefaction and saccharification stages starch are generally recommended for starch hydrolysis and are well known from the skilled person.

    On effectue la saccharification à la β-amylase associée éventuellement à l'enzyme débranchante jusqu'à ce que l'hydrolysat de maltose contienne au moins 75 % en poids de maltose et, de préférence, environ 80 % en poids de maltose. Elle dure au moins 24 heures.Β-amylase saccharification is carried out possibly associated with the disconnecting enzyme until the maltose hydrolyzate contains at least 75% by weight of maltose and preferably about 80% by weight maltose. It lasts at least 24 hours.

    L'hydrolysat ainsi saccharifié est ensuite filtré sur filtre à précouche ou par microfiltration sur membranes, puis déminéralisé et concentré.The hydrolyzate thus saccharified is then filtered on pre-layer or microfiltration filter on membranes, then demineralized and concentrated.

    A ce stade du procédé conforme à l'invention, on effectue un tamisage moléculaire du lait d'amidon liquéfié et saccharifié de manière à recueillir une fraction enrichie en maltose et une fraction enrichie en glucose. A la suite de quoi, on met en contact la fraction enrichie en maltose avec une α-amylase maltogénique Cette dernière est avantageusement celle commercialisée par la société NOVO, sous les noms Maltogénase® 4000L et NOVAMYL®.At this stage of the process according to the invention, it is performs molecular sieving of liquefied starch milk and saccharified so as to collect a fraction enriched in maltose and a fraction enriched in glucose. AT following which, the fraction enriched in maltose with a maltogenic α-amylase The latter is advantageously that marketed by the company NOVO, under the names Maltogenase® 4000L and NOVAMYL®.

    L'étape de tamisage moléculaire mise en oeuvre dans le procédé conforme à l'invention peut consister, par exemple, en une étape de séparation chromatographique ou en une étape de séparation sur membranes.The molecular sieving step implemented in the process according to the invention may consist, for example, in a chromatographic separation step or in a separation step on membranes.

    L'étape de fractionnement chromatographique est effectuée de manière connue en soi, de façon discontinue ou continue (lit mobile simulé), sur des adsorbants du type résines cationiques, ou sur des zéolithes fortement acides, chargées préférentiellement à l'aide d'ions alcalins ou alcalino-terreux tels que le calcium ou le magnésium mais plus préférentiellement à l'aide d'ions sodium.The chromatographic fractionation step is carried out in a manner known per se, discontinuously or continuous (simulated moving bed), on adsorbents of the type cationic resins, or on strongly acidic zeolites, preferentially charged using alkaline ions or alkaline earth such as calcium or magnesium but more preferably using sodium ions.

    En lieu et place de l'étape de séparation chromatographique, il est possible, dans le procédé conforme à l'invention, de mettre en oeuvre une étape de séparation par nanofiltration sur membranes. Des membranes de différents diamètres de pores sont fabriquées à partir de nombreux polymères et copolymères du type polysulfones, polyamides, polyacrylonitrates, polycarbonates, polyfuranes, etc.In place of the separation step chromatographic it is possible in the process according to the invention, to implement a step of separation by nanofiltration on membranes. Membranes different pore diameters are made from many polymers and copolymers of the polysulfone type, polyamides, polyacrylonitrates, polycarbonates, polyfurans, etc.

    Des exemples de l'utilisation de telles membranes sont décrits notamment dans les documents US-A-4.511.654, US-A-4.429.122 et WO-A-95/10627.Examples of the use of such membranes are described in particular in documents US-A-4,511,654, US-A-4,429,122 and WO-A-95/10627.

    Selon un mode de réalisation avantageux du procédé conforme à l'invention, la partie non maltose issue des membranes ou de la chromatographie, comportant la fraction enrichie en glucose, est recyclée en amont de l'étape de saccharification.According to an advantageous embodiment of the method according to the invention, the non-maltose part from membranes or chromatography, comprising the fraction enriched in glucose, is recycled upstream of the saccharification.

    Grâce au procédé conforme à l'invention qui tire profit des bénéfices obtenus à la fois des étapes d'hydrolyse mises en oeuvre et de l'étape de tamisage moléculaire, il est possible d'obtenir, avec des rendements supérieurs à 90 %, un hydrolysat d'amidon dont la teneur en maltose est supérieure à 95 %, et même supérieure à 98 % lorsqu'une isoamylase est mise en oeuvre dans les étapes d'hydrolyse.Thanks to the process according to the invention which draws profit from the benefits obtained from both stages hydrolysis implemented and the sieving step molecular it is possible to get, with yields greater than 90%, a starch hydrolyzate with a content of maltose is more than 95%, and even more than 98% when an isoamylase is used in the steps hydrolysis.

    A ce stade du procédé conforme à l'invention, il est éventuellement possible d'effectuer sur l'hydrolysat (ou sirop de maltose) une cristallisation du maltose ou une hydrogénation catalytique.At this stage of the process according to the invention, it is possibly possible to perform on the hydrolyzate (or maltose syrup) a crystallization of maltose or a catalytic hydrogenation.

    L'hydrogénation d'un tel hydrolysat s'effectue conformément aux règles de l'art qui conduisent par exemple à la production de sorbitol à partir du glucose.The hydrogenation of such a hydrolyzate is carried out in accordance with the rules of the art which lead for example to the production of sorbitol from glucose.

    On peut utiliser pour cette étape aussi bien des catalyseurs à base de ruthénium que des catalyseurs au nickel de RANEY. On préfère cependant utiliser des catalyseurs au nickel de RANEY qui sont moins onéreux.We can use for this step as well ruthenium-based catalysts as RANEY nickel. However, we prefer to use RANEY nickel catalysts which are less expensive.

    Dans la pratique, on utilise de 1 à 10 % en poids de catalyseur par rapport à la matière sèche de l'hydrolysat soumis à l'hydrogénation. L'hydrogénation s'effectue de préférence sur un hydrolysat dont la matière sèche est comprise entre 15 et 50 %, dans la pratique voisine de 30 à 45 %, sous une pression d'hydrogène comprise entre 20 et 200 bars. Elle peut être effectuée de manière continue ou discontinue.In practice, from 1 to 10% by weight of catalyst relative to the dry matter of the hydrolyzate subject to hydrogenation. The hydrogenation takes place from preferably on a hydrolyzate whose dry matter is between 15 and 50%, in practice close to 30 to 45%, under a hydrogen pressure between 20 and 200 bars. It can be performed continuously or discontinuous.

    Lorsque l'on opère de manière discontinue, la pression d'hydrogène utilisée est généralement comprise entre 30 et 60 bars et la température à laquelle se déroule l'hydrogénation est comprise entre 100 et 150°C. On veille aussi à maintenir le pH du milieu d'hydrogénation par l'addition de soude ou de carbonate de soude par exemple, mais sans dépasser un pH de 9,0. Cette manière de faire permet d'éviter l'apparition de produits de cracking ou d'isomérisation.When operating discontinuously, the pressure of hydrogen used is generally between 30 and 60 bars and the temperature at which it takes place the hydrogenation is between 100 and 150 ° C. We watch also to maintain the pH of the hydrogenation medium by the addition of soda or sodium carbonate for example, but without exceeding a pH of 9.0. This way of doing things prevents the appearance of cracking products or isomerization.

    On arrête la réaction lorsque la teneur du milieu réactionnel en sucres réducteurs est devenue inférieure à 1 %, de préférence encore inférieure à 0,5 % et plus particulièrement inférieure à 0,1 %.The reaction is stopped when the content of the medium reaction in reducing sugars has become less than 1%, preferably still less than 0.5% and more particularly less than 0.1%.

    Après refroidissement du milieu réactionnel, on élimine le catalyseur par filtration et on déminéralise le sirop de maltitol ainsi obtenu sur des résines cationiques et anioniques. A ce stade, les sirops contiennent au moins 93 % de maltitol.After the reaction medium has cooled, remove the catalyst by filtration and demineralize the maltitol syrup thus obtained on cationic resins and anionic. At this point, the syrups contain at least 93% maltitol.

    Le sirop de maltitol obtenu à l'étape d'hydrogénation précédente peut alors subir une étape de cristallisation de manière à obtenir du maltitol cristallisé.The maltitol syrup obtained in the hydrogenation stage previous can then undergo a crystallization step of so as to obtain crystallized maltitol.

    Selon un mode de réalisation préféré conforme à l'invention, on met en oeuvre sur le sirop de maltitol obtenu à l'étape d'hydrogénation précédente, la succession des étapes suivantes consistant à :

    • concentrer le sirop de maltitol ;
    • cristalliser et séparer les cristaux de maltitol formés ;
    • effectuer sur les eaux-mères de cristallisation un tamisage moléculaire et, en particulier, un fractionnement chromatographique de manière à obtenir une fraction enrichie en maltitol et une fraction appauvrie en maltitol ;
    • recycler la fraction enrichie en maltitol en amont de l'étape de cristallisation ;
    • effectuer éventuellement sur la fraction appauvrie en maltitol, une hydrolyse acide et/ou une hydrolyse enzymatique au moyen par exemple d'une amyloglucosidase immobilisée ou non ;
    • effectuer éventuellement une hydrogénation de ladite fraction appauvrie en maltitol et hydrolysée en vue d'obtenir un sirop de sorbitol.
    According to a preferred embodiment in accordance with the invention, the maltitol syrup obtained in the preceding hydrogenation step is used, the succession of the following steps consisting in:
    • concentrate the maltitol syrup;
    • crystallize and separate the maltitol crystals formed;
    • carry out molecular sieving on the crystallization mother liquors and, in particular, chromatographic fractionation so as to obtain a fraction enriched in maltitol and a fraction depleted in maltitol;
    • recycling the maltitol-enriched fraction upstream of the crystallization step;
    • optionally carrying out on the maltitol-depleted fraction, an acid hydrolysis and / or an enzymatic hydrolysis by means for example of an immobilized or not immobilized amyloglucosidase;
    • optionally carrying out a hydrogenation of said fraction depleted in maltitol and hydrolyzed in order to obtain a sorbitol syrup.

    De manière surprenante et inattendue, l'utilisation selon l'invention de sirop riche en maltose pour la fabrication de maltitol cristallisé permet de diminuer de façon très importante (jusqu'à 80% par rapport à un procédé conventionnel) les quantités d'eaux-mères (i.e. la fraction appauvrie en maltitol) générées lors de l'étape de tamisage moléculaire en aval de l'étape de cristallisation.Surprisingly and unexpectedly, the use according to the invention of syrup rich in maltose for the manufacturing crystallized maltitol makes it possible to reduce very importantly (up to 80% compared to a process the quantities of mother liquors (i.e. the fraction depleted in maltitol) generated during the sieving step molecular downstream of the crystallization step.

    D'autres caractéristiques et avantages de l'invention apparaítront clairement à la lecture des exemples qui suivent. Ils ne sont toutefois donnés ici qu'à titre illustratif et non limitatif.Other characteristics and advantages of the invention will become clear on reading the examples which follow. They are however given here only as illustrative and not limiting.

    EXEMPLE 1EXAMPLE 1

    Un lait d'amidon, à une matière sèche de 31 %, est liquéfié de manière classique à l'aide de 0,2 % de TERMAMYL® 120L (α-amylase commercialisée par la société NOVO) à un pH de 5,7 à 6,5 jusqu'à un DE légèrement inférieur à 4. Starch milk, with a dry matter content of 31%, is conventionally liquefied using 0.2% TERMAMYL® 120L (α-amylase marketed by the company NOVO) at a pH of 5.7 to 6.5 to a slightly ED less than 4.

    On chauffe ensuite le milieu réactionnel pendant quelques secondes à 140°C de manière à inhiber l'α-amylase, puis on ajuste le pH entre 5 et 5,5 et la température à 55°C.The reaction medium is then heated for a few seconds at 140 ° C. so as to inhibit α-amylase, then we adjust the pH between 5 and 5.5 and the temperature at 55 ° C.

    La saccharification est conduite à une matière sèche de 25 %, ou légèrement inférieure, en présence de pullulanase (PULLUZYME® 750L commercialisée par la société ABM) et de β-amylase (SPEZYME® BBA commercialisée par la société GENENCOR) à des doses respectives de 0,1 % et 0,05 % sur matière sèche.The saccharification is carried out with a dry matter 25%, or slightly lower, in the presence of pullulanase (PULLUZYME® 750L sold by the company ABM) and β-amylase (SPEZYME® BBA marketed by the GENENCOR) at respective doses of 0.1% and 0.05 % on dry matter.

    La saccharification, qui dure environ 48 heures, donne un hydrolysat montrant la composition suivante, DP1 : 1,4 %, DP2 : 82,4 %, DP3 : 13,2 %, DP4 et plus : 2,6 %.The saccharification, which lasts about 48 hours, gives a hydrolyzate showing the following composition, DP1: 1.4 %, DP2: 82.4%, DP3: 13.2%, DP4 and more: 2.6%.

    L'hydrolysat subit ensuite une purification classique par filtration, décoloration et déminéralisation puis est concentré à environ 20 % de matière sèche et ajusté à pH 5,5.The hydrolyzate then undergoes a conventional purification by filtration, discoloration and demineralization then is concentrated to around 20% dry matter and adjusted to pH 5.5.

    On procède à une étape de chromatographie continue de l'hydrolysat de maltose ainsi obtenu de la manière suivante.A continuous chromatography step is carried out on the maltose hydrolyzate thus obtained in the manner next.

    Quatre colonnes d'un litre de résine PCR 732 sodique thermostatées à 75°C sont assemblées en série et alimentées en continu avec l'hydrolysat de maltose amené à une matière sèche de 60 % en poids, à un débit de 110 ml/h.Four one liter columns of PCR 732 sodium resin thermostatically controlled at 75 ° C are assembled in series and supplied continuously with the maltose hydrolyzate supplied to a material 60% by weight dry, at a flow rate of 110 ml / h.

    En sortie de colonne on récupère les fractions enrichies en maltose de composition suivante : DP1 : 1,5 %, DP2 : 94 %, DP3 : 4,5 %.Leaving the column, the fractions are recovered enriched with maltose of the following composition: DP1: 1.5%, DP2: 94%, DP3: 4.5%.

    Le rendement chromatographique en maltose est de 91,5 %.The chromatographic maltose yield is 91.5 %.

    Ces fractions sont concentrées à environ 20% de matière sèche et ajusté à pH 5, 5 puis sont mises en contact avec une α-amylase maltogénique (Maltogénase® 4000L commercialisée par la société NOVO) à une dose de 0,3% sur matière sèche. La composition du sirop de maltose obtenu est la suivante : DP1 : 4 %, DP2 : 95,5 %, DP3 : 0,5 %.These fractions are concentrated to around 20% of dry matter and adjusted to pH 5, 5 then put in contact with a maltogenic α-amylase (Maltogenase® 4000L marketed by the company NOVO) at a dose of 0.3% on dry matter. The composition of the maltose syrup obtained is as follows: DP1: 4%, DP2: 95.5%, DP3: 0.5%.

    EXEMPLE 2EXAMPLE 2

    Le sirop de maltose obtenu dans l'exemple 1 ci-dessus est soumis à une étape de cristallisation du maltose de la manière suivante. On prépare une solution de maltose d'une matière sèche de 75 % en poids à une température de 75°C. On ensemence la solution de maltose avec 5 % en poids de germes de cristaux de maltose et refroidit la solution de 75°C à 40°C, à raison de 0,5°C par heure, en agitant la solution à 50 tours/min dans un cristallisoir à double paroi.The maltose syrup obtained in Example 1 above is subjected to a maltose crystallization stage of the next way. A maltose solution of a dry matter of 75% by weight at a temperature of 75 ° C. The maltose solution is seeded with 5% by weight of maltose crystal sprouts and cools the solution 75 ° C to 40 ° C, 0.5 ° C per hour, shaking the solution at 50 rpm in a double crystallizer wall.

    En fin de cristallisation, les cristaux sont séparés de la liqueur mère à l'aide d'une essoreuse centrifuge conventionnelle.At the end of crystallization, the crystals are separated mother liquor using a centrifugal wringer conventional.

    Le rendement de cristallisation est de 50 % en poids exprimé en poids de maltose cristallisé sur le poids de maltose de départ. La pureté en maltose des cristaux récupérés est de 97,5 % sur sec. La teneur en eau est de 5%.The crystallization yield is 50% by weight expressed by weight of crystallized maltose on the weight of starting maltose. The maltose purity of the crystals recovered is 97.5% on dry. The water content is 5%.

    EXEMPLE 3EXAMPLE 3

    Le sirop de maltose issu de l'exemple 1 est déminéralisé puis hydrogéné dans les conditions suivantes : Matière sèche 40 % Température 115°C Dose de catalyseur 5 % P/P sec Pression d'H2 50 bars The maltose syrup from Example 1 is demineralized and then hydrogenated under the following conditions: Dry matter 40% Temperature 115 ° C Catalyst dose 5% dry P / P H 2 pressure 50 bars

    On arrête la réaction quand les sucres réducteurs sont inférieurs à 0,3 %. Le milieu est alors filtré, déminéralisé et concentré à 85 % de matière sèche ; sa composition est : Sorbitol 5,5 % Maltitol 94,0 % Supérieurs hydrogénés 0,5 % The reaction is stopped when the reducing sugars are less than 0.3%. The medium is then filtered, demineralized and concentrated to 85% dry matter; its composition is: Sorbitol 5.5% Maltitol 94.0% Hydrogenated superiors 0.5%

    On procède alors à l'étape de cristallisation par refroidissement de 75 à 25°C, à raison de 0,5°C/heure sous agitation lente, avec amorçage de 6 % P/P sec de maltitol cristallisé de granulométrie comprise entre 200 et 250µm.We then proceed to the crystallization step by cooling from 75 to 25 ° C, at a rate of 0.5 ° C / hour under slow agitation, with priming of 6% w / w dry maltitol crystallized with a particle size between 200 and 250 µm.

    Après turbinage, les cristaux sont séchés et présentent une richesse de 99,7 % ; les eaux-mères sont ajustées à 60 % de matière sèche et chromatographiées.After turbination, the crystals are dried and have a richness of 99.7%; the mother liquors are adjusted to 60% dry matter and chromatographed.

    Quatre colonnes d'un litre de résine PCR732, sous forme calcium, thermostatées à 85°C sont assemblées en série et alimentées de façon continue à un débit de 120 ml/h. Le rendement en maltitol est de 90,7 % et la fraction noble (fraction riche en maltitol) présente la composition suivante : sorbitol 4,5 % ; maltitol 95 % ; supérieurs hydrogénés : 0,5 %Four columns of a liter of PCR732 resin, under calcium form, thermostatically controlled at 85 ° C are assembled in series and continuously fed at a flow rate of 120 ml / h. The maltitol yield is 90.7% and the fraction noble (fraction rich in maltitol) has the composition following: sorbitol 4.5%; maltitol 95%; superiors hydrogenated: 0.5%

    La fraction appauvrie en maltitol, contenant 53,5 % de sorbitol, 42,5 % de maltitol et 4 % de supérieurs hydrogénés, est ensuite soumise à une étape d'hydrolyse acide.The maltitol-depleted fraction, containing 53.5% of sorbitol, 42.5% maltitol and 4% superior hydrogenated, is then subjected to a hydrolysis step acid.

    L'hydrolyse de la fraction appauvrie est réalisée en continu, sur une résine échangeuse de cations, de type C145 de Purolite, sous forme H+ placée dans une colonne thermostatée à 115°C ; en alimentant la colonne à 1 bv/h avec la solution concentrée à 40 %, la composition suivante est obtenue : sorbitol : 70,5 % ; maltitol : 12,3 % ; supérieurs : 0,4 % ; glucose : 16,8 %.The hydrolysis of the depleted fraction is carried out continuously, on a cation exchange resin, of type C145 from Purolite, in H + form placed in a column thermostatically controlled at 115 ° C; by feeding the column at 1 bv / h with the concentrated solution at 40%, the following composition is obtained: sorbitol: 70.5%; maltitol: 12.3%; higher: 0.4%; glucose: 16.8%.

    Cette solution est ensuite déminéralisée et hydrogénée dans les conditions suivantes : Matière sèche 40 % Température 135°C Dose de catalyseur 5 % P/Psec Pression d'hydrogène 50 bars,    jusqu'à obtenir un taux de sucres réducteurs libres inférieur à 0,1 %.This solution is then demineralized and hydrogenated under the following conditions: Dry matter 40% Temperature 135 ° C Catalyst dose 5% P / Psec Hydrogen pressure 50 bars, until a rate of free reducing sugars of less than 0.1% is obtained.

    Claims (6)

    Procédé de fabrication d'un sirop riche en maltose, comprenant les étapes successives consistant à : (a) effectuer une liquéfaction d'un lait d'amidon ; (b) effectuer une saccharification du lait d'amidon liquéfié en présence d'une β-amylase et d'au moins une enzyme débranchante choisie dans le groupe constitué par les pullulanases et les isoamylases ; (c) effectuer un tamisage moléculaire du lait d'amidon liquéfié et saccharifié de manière à recueillir une fraction enrichie en maltose et une fraction enrichie en glucose ; (d) mettre en contact ladite fraction enrichie en maltose avec une α-amylase maltogénique en vue de l'obtention d'un sirop riche en maltose. Process for the manufacture of a syrup rich in maltose, comprising the successive stages consisting in: (a) carrying out a liquefaction of a starch milk; (b) carrying out a saccharification of the liquefied starch milk in the presence of a β-amylase and at least one debranching enzyme chosen from the group consisting of pullulanases and isoamylases; (c) carrying out molecular sieving of the liquefied and saccharified starch milk so as to collect a fraction enriched in maltose and a fraction enriched in glucose; (d) bringing said maltose-enriched fraction into contact with a maltogenic α-amylase with a view to obtaining a syrup rich in maltose. Procédé de fabrication d'un sirop riche en maltose, comprenant les étapes successives consistant à : (a) effectuer une liquéfaction d'un lait d'amidon ; (b) effectuer une saccharification du lait d'amidon liquéfié en présence d'une β-amylase ; (c) effectuer un tamisage moléculaire du lait d'amidon liquéfié et saccharifié de manière à recueillir une fraction enrichie en maltose et une fraction enrichie en glucose ; (d) mettre en contact ladite fraction enrichie en maltose avec une α-amylase maltogénique et au moins une enzyme débranchante choisie dans le groupe constitué par les pullulanases et les isoamylases en vue de l'obtention d'un sirop riche en maltose. Process for the manufacture of a syrup rich in maltose, comprising the successive stages consisting in: (a) carrying out a liquefaction of a starch milk; (b) carrying out a saccharification of the liquefied starch milk in the presence of a β-amylase; (c) carrying out molecular sieving of the liquefied and saccharified starch milk so as to collect a fraction enriched in maltose and a fraction enriched in glucose; (d) bringing said maltose-enriched fraction into contact with a maltogenic α-amylase and at least one debranching enzyme chosen from the group consisting of pullulanases and isoamylases with a view to obtaining a syrup rich in maltose. Procédé de fabrication de maltose cristallisé par cristallisation d'un sirop riche en maltose, caractérisé par le fait que le sirop riche en maltose est obtenu par la mise en oeuvre d'un procédé conforme à la revendication 1 ou 2. Process for manufacturing crystallized maltose by crystallization of a syrup rich in maltose, characterized by the fact that the maltose-rich syrup is obtained by implementing a process in accordance with claim 1 or 2. Utilisation d'un sirop riche en maltose obtenu par la mise en oeuvre d'un procédé conforme à la revendication 1 ou 2 pour la fabrication d'un sirop riche en maltitol, par hydrogénation du sirop riche en maltose.Use of a syrup rich in maltose obtained by implementing a process in accordance with claim 1 or 2 for the manufacture of a rich syrup into maltitol, by hydrogenation of the syrup rich in maltose. Utilisation d'un sirop riche en maltose obtenu par la mise en oeuvre d'un procédé conforme à la revendication 1 ou 2 pour la fabrication de maltitol cristallisé, par hydrogénation du sirop riche en maltose en sirop riche en maltitol, puis par cristallisation du sirop riche en maltitol.Use of a syrup rich in maltose obtained by implementing a process in accordance with claim 1 or 2 for the manufacture of maltitol crystallized, by hydrogenation of the maltose-rich syrup in syrup rich in maltitol, then by crystallization of the syrup rich in maltitol. Utilisation selon la revendication 5, caractérisée par le fait qu'elle comprend les étapes consistant à : (a) cristalliser le sirop riche en maltitol ; (b) effectuer un tamisage moléculaire des eaux-mères de cristallisation de manière à recueillir une fraction enrichie en maltitol et une fraction appauvrie en maltitol ; (c) recycler ladite fraction riche en maltitol en amont de l'étape de cristallisation ; (d) effectuer une hydrolyse acide et/ou enzymatique de ladite fraction appauvrie en maltitol ; (e) effectuer une hydrogénation de ladite fraction appauvrie en maltitol et hydrolysée. Use according to claim 5, characterized in that it comprises the steps consisting in: (a) crystallizing the maltitol-rich syrup; (b) carrying out molecular sieving of the crystallization mother liquors so as to collect a fraction enriched in maltitol and a fraction depleted in maltitol; (c) recycling said maltitol-rich fraction upstream of the crystallization step; (d) carrying out an acidic and / or enzymatic hydrolysis of said maltitol-depleted fraction; (e) carrying out a hydrogenation of said fraction depleted in maltitol and hydrolyzed.
    EP99403287A 1998-12-29 1999-12-27 Process for producing a syrup rich in maltose Expired - Lifetime EP1016728B1 (en)

    Applications Claiming Priority (2)

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    FR9816539A FR2787809B1 (en) 1998-12-29 1998-12-29 PROCESS FOR THE MANUFACTURE OF A MALTOSE-RICH SYRUP
    FR9816539 1998-12-29

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    EP1016728A3 EP1016728A3 (en) 2001-03-14
    EP1016728B1 EP1016728B1 (en) 2005-04-20

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    EP (1) EP1016728B1 (en)
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    AT (1) ATE293703T1 (en)
    AU (1) AU6544199A (en)
    BR (1) BR9907436A (en)
    CA (1) CA2296198A1 (en)
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    Cited By (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    WO2002053782A1 (en) * 2000-12-28 2002-07-11 Danisco Sweeteners Oy Process for purifying maltose
    US6436678B2 (en) 2000-02-28 2002-08-20 Grain Processing Corporation High purity maltose process and products
    WO2008029033A1 (en) 2006-09-08 2008-03-13 Syral Methodfor production of a syrup with a high maltitol content

    Families Citing this family (17)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    JP2004504852A (en) * 2000-07-28 2004-02-19 ノボザイムス　アクティーゼルスカブ Method for producing maltose syrup using hexosyltransferase
    FI20020675A0 (en) * 2002-04-09 2002-04-09 Danisco Sweeteners Oy Purification of a pure disaccharide solution
    US20040224058A1 (en) * 2003-03-20 2004-11-11 Spi Polyols, Inc. Maltitol solutions with high maltitol content and methods of making same
    CA2529508C (en) * 2003-07-18 2013-08-27 Cargill Incorporated Process for preparing maltitol enriched products
    KR20080049924A (en) * 2006-12-01 2008-06-05 주식회사 신동방씨피 Process for preparing high purity maltitol crystalline powder
    KR101445432B1 (en) * 2008-01-04 2014-09-26 콘 프러덕트 인터내셔널, 인코포레이티드 Process for the preparation of isomaltooligosaccharide-hydrogenated
    US9816119B2 (en) * 2008-02-29 2017-11-14 Syngenta Participations Ag Methods for starch hydrolysis
    FR2943686B1 (en) * 2009-03-30 2013-11-01 Roquette Freres PROCESS FOR OBTAINING BETA AMYLASE PREPARATION FROM SOLUBLE FRUITS OF STARCH PLANTS
    EP2809793B1 (en) * 2012-01-31 2019-10-30 Cargill, Incorporated Process for producing maltitol from starch
    CN104136621B (en) * 2012-01-31 2021-01-26 卡吉尔公司 Method for producing solid maltitol from starch
    MX2014009226A (en) * 2012-01-31 2014-11-10 Cargill Inc Process for producing maltose from starch.
    EP2831259A1 (en) 2012-03-28 2015-02-04 Danisco US Inc. Method for making high maltose syrup
    CN103409484B (en) * 2013-08-23 2015-03-11 山东福田药业有限公司 Preparation method of superhigh malt syrup
    AU2017295412B2 (en) * 2016-07-15 2022-02-03 Novozymes A/S Improving the rollability of flat breads
    CN113322292A (en) * 2021-04-12 2021-08-31 双桥（厦门）有限公司 Preparation process of syrup suitable for liquid cod liver oil and liquid cod liver oil
    CN114150028A (en) * 2021-11-27 2022-03-08 湖北德安府糖业股份有限公司 Preparation process of fermented maltose syrup
    CN114249780B (en) * 2021-12-23 2023-07-21 浙江华康药业股份有限公司 Method for preparing liquid maltitol and liquid polyol by using maltitol chromatographic raffinate

    Citations (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    FR2012831A1 (en) * 1968-07-12 1970-03-27 Hayashibara Co
    US4846139A (en) * 1984-12-20 1989-07-11 Roquette Freres Process for the preparation of crystalline maltitol
    EP0816373A1 (en) * 1996-07-05 1998-01-07 Towa Chemical Industry Co., Ltd. A process for manufacturing crystalline maltitol and crystalline mixture solid containing the same
    EP0905256A1 (en) * 1997-09-26 1999-03-31 Roquette Frˬres Process for producing a syrup rich in maltose

    Family Cites Families (6)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3708396A (en) 1968-01-23 1973-01-02 Hayashibara Co Process for producing maltitol
    JPS5577896A (en) 1978-12-07 1980-06-12 Meiji Seika Kaisha Ltd Preparation of high-purity maltose
    US4429122A (en) 1982-04-20 1984-01-31 Uop Inc. Separation of saccharides
    US4487198A (en) 1982-07-28 1984-12-11 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Process for producing a high-purity maltose
    JP2696534B2 (en) * 1988-09-29 1998-01-14 東和化成工業株式会社 Process for producing high-purity maltose and its reduced product
    JP2696537B2 (en) * 1988-10-28 1998-01-14 東和化成工業株式会社 Method for producing high-purity maltose

    Patent Citations (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    FR2012831A1 (en) * 1968-07-12 1970-03-27 Hayashibara Co
    US4846139A (en) * 1984-12-20 1989-07-11 Roquette Freres Process for the preparation of crystalline maltitol
    EP0816373A1 (en) * 1996-07-05 1998-01-07 Towa Chemical Industry Co., Ltd. A process for manufacturing crystalline maltitol and crystalline mixture solid containing the same
    EP0905256A1 (en) * 1997-09-26 1999-03-31 Roquette Frˬres Process for producing a syrup rich in maltose

    Non-Patent Citations (2)

    * Cited by examiner, † Cited by third party
    Title
    DATABASE WPI Section Ch, Week 9019 Derwent Publications Ltd., London, GB; Class D16, AN 90-144908 XP002114479 & JP 02 092296 A (TOWA KASEI KOGYO KK), 3 avril 1990 (1990-04-03) *
    DOYLE E M ET AL: "Mechanisms of action of the maltogenic alpha amylase of Byssochlamys fulva." ENZYME AND MICROBIAL TECHNOLOGY, vol. 22, no. 7, 15 mai 1998 (1998-05-15), pages 612-616, XP002114478 Dep. of Ind. Microbiol., Univ. Coll. Dublin, Belfield, Dublin, Republic of Ireland *

    Cited By (6)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US6436678B2 (en) 2000-02-28 2002-08-20 Grain Processing Corporation High purity maltose process and products
    US6670155B2 (en) 2000-02-28 2003-12-30 Grain Processing Corporation Process for preparing dextrins
    WO2002053782A1 (en) * 2000-12-28 2002-07-11 Danisco Sweeteners Oy Process for purifying maltose
    US6692577B2 (en) 2000-12-28 2004-02-17 Danisko Sweeteners Oy Process for purifying maltose
    WO2008029033A1 (en) 2006-09-08 2008-03-13 Syral Methodfor production of a syrup with a high maltitol content
    FR2905705A1 (en) * 2006-09-08 2008-03-14 Syral PROCESS FOR OBTAINING A SYRUP HAVING HIGH MALTITOL CONTENT AND SYRUP THUS OBTAINED

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    JP2000189184A (en) 2000-07-11
    US20020055150A1 (en) 2002-05-09
    AU6544199A (en) 2000-07-06
    EP1016728A3 (en) 2001-03-14
    EP1016728B1 (en) 2005-04-20
    KR20000052608A (en) 2000-08-25
    US6346400B1 (en) 2002-02-12
    BR9907436A (en) 2001-04-24
    FR2787809A1 (en) 2000-06-30
    FR2787809B1 (en) 2002-01-18
    ATE293703T1 (en) 2005-05-15
    CA2296198A1 (en) 2000-06-29
    DE69924821D1 (en) 2005-05-25

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